CN107567479B

CN107567479B - Self-cleaning composite material for producing moulded kitchen and bathroom upholstery

Info

Publication number: CN107567479B
Application number: CN201680026002.5A
Authority: CN
Inventors: A·布乔拉齐奥; M·S·皮亚内西; S·罗西尼
Original assignee: Delta Srl
Current assignee: Delta Srl
Priority date: 2015-05-06
Filing date: 2016-05-02
Publication date: 2020-04-10
Anticipated expiration: 2036-05-02
Also published as: WO2016177662A1; PL3292167T3; EP3292167B8; ITUB20150293A1; SI3292167T1; US10519294B2; CN107567479A; IL255281A0; ES2732471T3; US20180127563A1; RS58569B1; EP3292167B1; RU2687917C1; EP3292167A1

Abstract

一种自清洁复合材料，其包含以下组合物：50重量％～85重量％的三水合氧化铝(ATH)类矿物填充料；10％～30％的包含聚酯树脂的交联聚合物；相对于交联聚合物的重量以0.05％～5％的重量百分比分散在交联聚合物中的光催化性二氧化钛(TiO₂)；用于锚定在光催化性TiO₂与交联聚合物之间的相容剂，其中所述TiO₂的锚定相容剂是硅烷；和交联单体，用于通过热或化学聚合获得交联聚合物的网状结构。A self-cleaning composite material, comprising the following composition: 50% to 85% by weight of alumina trihydrate (ATH)-based mineral filler; 10% to 30% of a cross-linked polymer comprising polyester resin; relative Photocatalytic titanium dioxide (TiO ₂ ) dispersed in the cross-linked polymer at a weight percent of 0.05% to 5% based on the weight of the cross-linked polymer; for anchoring between the photocatalytic TiO ₂ and the cross-linked polymer The compatibilizer, wherein the anchor compatibilizer of TiO ₂ is a silane; and a crosslinking monomer for obtaining the network structure of the crosslinked polymer by thermal or chemical polymerization.

Description

Self-cleaning composite material for producing moulded kitchen and bathroom upholstery

Technical Field

The present patent application for industrial invention relates to a self-cleaning composite material for the production of moulded kitchen and bathroom upholstery items, such as sinks, work tables, wash basins, bathtubs, upholstery and the like.

Background

WO2013/017651 patent application in the name of the same applicant discloses a self-cleaning composite material having a core comprising a quartz-based mineral filler (charge) and photocatalytic nano-titanium dioxide (TiO)₂) The composition of (1), which is mixed in a methacrylic syrup containing methyl methacrylate MMA and polymethyl methacrylate PMMA. This composition is mixed with some mineral fillers and other chemicals, and the resulting mixture is cast or injected into a mold to obtain the finished product by polymerization.

The above-mentioned patent application WO2013/017651, using quartz-like minerals and methacrylic syrup consisting of one monomer and one polymer, discloses a material which can also be used in kitchen applications requiring high mechanical resistance, since the surface is subjected to high mechanical, chemical and physical stresses caused by kitchen tools such as pans, chopping boards, knives and tableware. However, the products obtained according to WO2013/017651 have the typical characteristics of thermosetting materials; as the liquid mixture polymerizes and becomes a solid composite, the surface and shape are imparted during molding.

The surface of the product is completely uniform, and the product can be used at any time without any additional treatment. However, after the product is removed from the mold, it is impossible to perform a repair or polishing operation. The drilling or cutting operations must be performed using machines with industrial diamond tools with MOHS 10 hardness, since their hardness must be higher than that of quartz with MOHS hardness of about 7.

Thus, the quartz mineral filler makes the final product very hard, without forgeability and complex moldability. The term "mouldable" means that the resin is converted into a composite material according to the prior art. Manufacturers of molded articles made of hard materials use quartz as the mineral filler because the surface must withstand impacts, shocks and surface scratches. Thus, if the final product is damaged or fails, it cannot be repaired.

Methacrylic slurries containing MMA require complex moulding know-how; in fact, special molds and elaborate molding processes must be used.

Furthermore, the mixture of the quartz mineral filler and the methacrylic syrup containing MMA produces a network of highly chemically bonded and highly cross-linked quartz mineral filler due to the presence of the cross-linking agent, thus making the final product impossible to thermoform or process.

Disclosure of Invention

The object of the present invention is to eliminate the drawbacks of the prior art by providing a self-cleaning composite material for manufacturing kitchen and bathroom upholstery products which are soft enough and easy to form for easy processing and repair.

It is a further object of the present invention to provide a self-cleaning composite material which can be thermoformed and molded easily with a particularly simple mold and a simple forming process.

It is another object of the present invention to provide a self-cleaning composite material which is photocatalytic in nature, effective, efficient, and at the same time environmentally friendly and non-toxic to humans and the environment.

These objects are achieved by the solution of the present invention.

In this specification, percentages are to be considered as weight percentages relative to the final product, unless percentages are indicated.

The composite material according to the invention has the following composition:

50-85 wt% of an Alumina Trihydrate (ATH) -based mineral filler having a size of 10-50 μm,

10-30% of polyester resin;

photocatalytic titanium dioxide (TiO) dispersed in a methacrylic syrup in an amount of 0.05 to 5 wt% based on the weight of the polyester resin₂)；

Compatibilisers, e.g. silanes, for applying photocatalytic TiO₂Anchored to the polyester resin; and

crosslinking monomers for obtaining a network structure of the polyester resin or the mixture.

Preferably, the polyester resin may be used alone. In fact, polyester resins can be easily polymerized at room temperature with known catalysts. The molding process of polyester resin is simple and requires a simple and inexpensive mold.

After some experimental tests, the applicant found that TiO can also be obtained using polyester resins₂The network structure of (2). In addition, the polyester resin is stable and TiO is added₂And then also remains stable.

Advantageously, polyester resins of the POLYLITE 32166-16REICHHOLD type may be used.

32166 is a polyester resin based on isophthalic acid and neopentyl glycol, having low viscosity, high solid content and low content of styrene.

32166 the polyester resin is a casting resin developed for producing materials that do not require covering with a gel coat. These resins are hard, of moderate reactivity and low viscosity. They are UV stable.

32166 the polyester resin can undergo deterioration caused by water, has good stain resistance, very high heat distortion temperature, high thermal shock property, and high resistance to many organic and inorganic solutions and solvents.

Instead of the polyester resin, a mixture of polyester resin and Methyl Methacrylate (MMA) may be used.

Polyester resins are poor in light resistance and tend to yellow after prolonged exposure to ultraviolet radiation. The addition of MMA in an amount of 0.5 to 15% to the polyester resin reduces or almost eliminates this phenomenon.

The use of MMA in the polyester makes the structure of the composite perform better in terms of mechanical properties. Furthermore, the use of MMA reduces the post-cure time of the polyester product, since MMA significantly enhances crosslinking during polymerization compared to styrene typically used in polyester resins.

However, the weight percentage of MMA in the mixture must be less than 15% of the total weight of the mixture. Therefore, the amount of polyester resin must be higher than 85% with respect to the total weight of the mixture. This ensures the above-mentioned advantages associated with polyester resins.

Alumina Trihydrate (ATH) has a MOHS hardness of less than 5, so that the final product is sufficiently soft, malleable, repairable and machinable, like wood, that is to say by tools commonly used by carpenters. In view of the above, if the final product is damaged, the damage can be repaired by mechanical operations (for example grinding and filling with special glues that can be sandblasted and polished after hardening), thus perfectly repairing the damaged, broken or defective parts.

Alumina Trihydrate (ATH) must have a size of 10-50 microns in order to have a homogeneous, dense material with rheological properties suitable for low pressure casting in a mold without sedimentation or sedimentation gradients of the mineral filler.

Albeit TiO₂An effective network can be formed with polyester resin, but when ATH is used, it is necessary to check whether the network prevents the thermoformability of the final product and the ease of repair with suitable glues or fillers. Experimental tests have shown that the final product obtained after moulding is still thermoformable.

Optionally, a siliceous type (SiO) with a size of less than 0.1mm may be added to the composition in an amount of 2% to 15% relative to the composition₂) The mineral filler of (1). For example, in the siliceous type (SiO)₂) The mineral fillers of (2) can be cristobalite, calcium silicate, wollastonite and/or feldspar, solid and hollow (open) glass microspheres.

Non-metallic mineral fillers that may be used include white talc, quartz sand, siliceous sand, carbonate sand, calcium carbonate, marble particles, through-hole quartz, barite, kaolin, hydrated alumina, hydrated calcium borate, alumina trihydrate, mica, alumina, aluminum sesquioxide, magnesium oxide, wollastonite, feldspar, virgin ground glass, and solid and hollow (open) glass microspheres.

In addition, virgin or recycled mineral fillers may be added. The mineral filler is recovered from fillers for processing ATH materials, quartz ceramics and recycled glass, or from fillers for underground water trough waste.

The dispersion is obtained by mixing the materials of a composition containing photocatalytic nano TiO chemically and intimately bound to the composition structure₂Thereby rendering the entire dispersion photocatalytic at the surface and inside.

The product obtained by polymerizing the dispersion is a composite of polyester resin with soft mineral filler (MOHS hardness below 5). This product is a highly innovative product and is not precedent in the market at present, since it is a flexible product that can be easily processed, repaired and thermoformed, in addition to having specific intrinsic photocatalytic properties.

It must be considered that polyester resins do not require any special molding know-how or skill, as this technology has been studied and used for many years. The molding of the polyester resin uses a simple system and a known catalyst. The moulds for processing the polyester dispersions are very simple to make (using epoxy or polyester resins or polyethylene with glass fibre reinforcement), do not have to be structured and are advantageously inexpensive.

Using Alumina Trihydrate (ATH) as the mineral filler, the end product is a composite material that can be easily used with common carpenter tools such as saws; in addition, the surface may be sandblasted or polished with conventional sandblasting and polishing paper. The surface may be cut, rounded, filled, polished, thermoformed, perforated, sandblasted and glued.

The product according to the invention has unique properties as a tough resin which is very easy to process, which allows the formation of a surface with no knots or with hardly noticeable knots. The velvet-like surface is visually pleasing and warm to the touch. The surface can be renewed and restored to the original state with a normal mild abrasive cleaner and abrasive sponge. The surface may be sanded to matte or polished to a mirror finish.

This material is easy and quick to maintain. It can be cleaned with soapy water or ordinary detergents to remove most stains or soils deposited on its surface. It is recommended to rinse the surface thoroughly with a gel or abrasive cleaner, using an abrasive sponge; in this way, the original matte surface will be maintained. As a material of uniform overall thickness, which can prevent surface erosion such as scratches, fume and smudge, the aesthetic appearance of the original surface can be restored by simply following these instructions; small surface damage can be repaired with abrasive sponges and ordinary abrasive cleaners. By polishing the surface of the damaged portion, the surface can be treated again with very fine grit blasting paper if the defects are still visible.

Drawings

Additional features of the invention will become clearer from the following description, given by way of example only and not by way of limitation, with reference to the embodiments illustrated in the accompanying drawings, in which:

FIG. 1 shows the reaction of TiO₂Anchored to the polyester resin;

FIG. 2 is a graph showing the Δ E trend of methylene blue measured with a colorimeter in three samples after exposure to a xenon lamp;

FIG. 3 is a graph showing the Δ E trend of eosin measured with a colorimeter in three samples after exposure to a xenon lamp; and

figure 4 is a graph showing the viscosity trend of three samples over time.

Detailed Description

The production process of the self-cleaning material provides for the incorporation of TiO into the material₂A first step of adding the active ingredient to the polyester resin. This step is carried out by determining the concentration of the photocatalytic TiO compound₂Compatible anchoring agent consisting of an anchoring silanating agent forming covalent bonds with the polyester resin, the TiO being covalently bound₂The composite structure of the active ingredient and the polyester resin is separately anchored and processed.

The silane being a result of TiO₂The reason for the silanization reaction by the covalent bond with the polyester substrate. This bond ensures that the TiO is bonded via a strong irreversible bond₂Anchored to the structure.

The silane was completely dispersed in the polyester resin by stirring at 900rpm for 10 minutes. Next, photocatalytic TiO is added to the polyester resin₂In order to obtain the best possible dispersion. Such formulations were kept dispersed for 2.5 hours at 900rpm with a screw stirrer. The speed was then increased to 1800rpm for 30 minutes to ensure TiO₂Complete dispersion in polyester resin.

The time required for the functionalization, that is to say for the silanization of the photocatalytic titanium, is about 3 hours. After such a reaction time, the remaining components may be added.

FIG. 1 shows the reaction of TiO₂Anchored to the polyester resin.

After anchoring the titanium oxide to the siloxane (silosanic) functional groups of the silane, all other components are added, starting with Alumina Trihydrate (ATH) mineral filler, followed by a cross-linking agent.

This filler dispersion was stirred with a screw stirrer at 900rpm for 2.5 hours and at 1800rpm for 30 minutes.

The final dispersion is placed in a mold and polymerized thermally or chemically at ambient temperature.

In the aspect of heating, the material is heated for a period of 30-40 minutes from the ambient temperature of 25-30 ℃, then the temperature is raised to 100 ℃ by a heating gradient, and cooling is carried out according to the type of the dispersion and the constant temperature system of the die.

Table 1 shows an example of a typical heat cycle for a strongly filled polyester dispersion.

Time (minutes)	Temperature of
		0	30℃
0～60	65℃
		8 hours	100℃

TABLE 1

Chemically, the polymerization is carried out by a series of suitable catalysts that start the reaction at ambient temperature, using the same formulation/chemical composition.

TBPM Tert-butyl Peroxymaleate PM-25 from Pergan PEROXAN

·Ca(OH)₂

Produced by BRUNO BOCK

PETMP pentaerythritol tetrakis (3-mercaptopropionate).

The same aesthetic, mechanical and chemical results were obtained in two different chemical and thermal polymerizations.

Photocatalytic TiO₂The functionalized polyester resins show excellent results in the degradation of various organic molecules such as oleic acid and colorants such as eosin Y, methylene blue and red methyl. In the presence of 3- (trimethoxysilyl) propyl methacrylate siloxane (silossanic) functional groups, it may be reacted by TiO₂The mass dispersion yields a filler polymer material with a self-cleaning surface.

The siloxane (silosanic) group allows for the incorporation of TiO₂Anchored to the polyester resin structure and at the same time acting as a dispersant; in this way, TiO₂Dispersed throughout the material on the surface and in the body.

Alumina Trihydrate (ATH) mineral filler particles having a size of less than 0.1mm provide suitable uniformity to the dispersion composition and facilitate a uniform surface when formed.

Advantageously, TiO₂Is in anatase form and is in powder form, having a nanoparticle size below 300 nm.

Advantageously, the polymeric portion consists solely of polyester resin.

Methacrylic monomers such as Methyl Methacrylate (MMA) may be added to the polyester resin at a weight percentage of less than 15% compared to the weight of the polyester resin and MMA mixture.

Preferably, the compatible anchor is a silane, which is equal to TiO₂Is added to the mixture; to ensure the photocatalyst (TiO)₂) Can be dispersed completely with TiO₂Compared to double the amount.

If the compatibilizer is trimethoxy silane, the silanization catalyst, Isopropylamine (IPA) and methacrylic acid (AMA) are used in equal amounts.

The invention is characterized by photocatalytic titanium dioxide (TiO)₂) Dispersion in polyester resin and methyl propylPolyester obtained by continuously polymerizing methyl enoate and mineral filler. Thus, after addition of inorganic material (e.g. Alumina Trihydrate (ATH) mineral filler, which is the majority of the final product), crosslinked resin and photocatalytic TiO-containing filler₂The resin (2) was subjected to the following comparative study and test.

Photocatalytic degradation only by TiO found on the surface of polymeric materials₂The process is carried out. TiO 2₂Is a heterogeneous catalyst that, when activated by light, produces a range of oxygenated active species, such as O, suitable for degradation of most organic species₂ ^-OH and H₂O₂. Thus, TiO₂Only acts as a catalyst and does not directly participate in the degradation process.

In view of the above, with TiO₂The preparation of the functionalized material was carried out by mixing the various organic components as follows:

organic moieties

-methacrylic acid slurry: methyl Methacrylate (MMA)/polymethyl methacrylate (PMMA)

Or

POLYLITE 32166-16REICHHOLD TYPE POLYLITE

Or

Polyester resin POLYLITE 32166-16REICHHOLD type and methyl methacrylate MMA

A crosslinking agent:

-diethylene glycol dimethacrylate (EGDM);

-tetraethyleneglycol dimethacrylate (TEGDM);

-trimethylolpropane trimethacrylate (TMPTMA);

anchoring molecules

-3-methacryloxypropyltrimethoxysilane (silane);

silanization catalyst

-Isopropylamine (IPA);

-methacrylic acid (AMA);

releasing agent:

-stearic acid;

-zinc stearate;

family of mineral fillers

Silicates of virgin or recycled type (quartz, cristobalite, silicon, glass solid and/or empty open glass microspheres)

Virgin or recycled alumina (alumina trihydrate ATH, alumina).

The recovery may be internal and external. The mineral fillers recovered by re-using underground water tanks as an environmental protection are of the internal type, or by using mineral fillers recovered from other industries (such as the ceramics and mining industries, rather than from quartz, ATH or other raw mineral fillers) are of the external type.

The following are three examples of samples for various comparative tests with the prior art. The sample composition is characterized by an organic fraction, a mineral filler and TiO₂With the same amounts of crosslinker and silane.

Example 1(PMMA/MMA (syrup) + 0.3% TiO₂+ Quartz

(composition described in WO 2013/017651)

The following components were mixed in a 1000cc high density polyethylene vessel using a screw agitator (speed 900 to 1800 rpm):

305.00 g of high-purity methyl methacrylate;

-45 grams of methyl methacrylate polymer.

The mixture was stirred until complete dissolution of the PMMA polymethylmethacrylate polymer was obtained.

The following components were then added:

6 g of silane DYNASYLAN MEMO (3-trimethoxysilyl) propyl methacrylate;

3 g of TiO produced by DEGUSSA₂P-25；

The minimum mixing time was 2.5 hours, after which the following components were added:

620.36 g of quartz type mineral filler with a size of 0.1-0.6 mm and white color

4.00, 3.00, 12.00 grams of cross-linking agent, EGDM-TEGDM-TMPTM respectively;

0.60 g of zinc stearate.

As the silylation catalyst, 0.22 grams of a mixture of variable Amounts of Methacrylic Acid (AMA) and Isopropylamine (IPA) was used.

Prepared by mixing the above components in the following order: first, methyl methacrylate is mixed with polymethyl methacrylate (PMMA). The crosslinker (EGDM, TEGDM, TMPTM) and zinc stearate were then added and the dispersion was stirred for at least 2.5 hours. In this way, only the organic portion was mixed, then DYNASYLAN MEMO (3- (trimethoxysilyl) propyl methacrylate) was added, then P-25TiO was added₂AMA and IPA; in this way, the addition is made to be in contrast to TiO₂Before the mineral filler is supplied in excess, the TiO is ensured₂Interaction with siloxane functionality; the Ti-O-Si bonds are sufficiently strong to exclude quartz and siloxane functional groups (-Si (OCH)₃)₃) Thereby ensuring the photocatalytic TiO₂Anchored to the polymer structure.

Then, the mineral filler and zinc stearate are added and the dispersion is stirred or tumbled for at least 6 hours, which is the time required to recover the mineral filler for bonding and the siloxane functionality remaining free.

Then, 0.5% of Perkadox 16 polymerization catalyst and 0.15% of stearic acid as a mold release agent were added, and the solution was stirred at 1800rpm for 30 minutes.

The final dispersion was placed in a mold and thermally polymerized: the material is heated from an ambient temperature of 25-30 ℃, then raised to 100 ℃ with a heating gradient and cooled for an average time of 20-40 minutes, depending on the type of dispersion and the constant temperature time of the mold.

Then, the mineral filler and zinc stearate are added and the dispersion is stirred or rolled for at least 6 hours, which is the time required for the mineral filler to bond and the siloxane functionality to remain free.

Then, 0.5% of Perkadox 16 polymerization catalyst and 0.15% of stearic acid as a mold release agent were added, and the solution was stirred at 1800rpm for 30 minutes. The material is then cast in a mould and polymerized according to the prior art.

Example 2(polyester + 0.3% TiO)₂+ ATH) (inventive)

The following components were mixed in a 1000cc high density polyethylene vessel using a screw stirrer (900 to 1800 rpm):

420.00 g of polyester POLYLITE 32166-16 REICHHOLD;

6 g of silane DYNASYLAN MEMO 3-trimethoxysilyl) propyl methacrylate;

the following components were then added:

3 g of TiO produced by DEGUSSA₂P-25；

559.2 g of ATH (alumina trihydrate) mineral filler, size less than 50 μm

4.00, 3.00, 12.00 grams of cross-linking agent, EGDM-TEGDM-TMPTM respectively;

1.5 g of zinc stearate.

About 0.06 and 0.07 grams of a mixture of varying amounts of methacrylic acid and isopropylamine were used as the silylation catalyst.

Then, 0.5% of Luperox MEKP (methyl ethyl ketone peroxide) polymerization catalyst, 1.5% and 0.15% of stearic acid as a mold release agent were added, and the solution was stirred at 1800rpm for 15 minutes. Casting the material in a mould and polymerising with water at a constant temperature of 65 ℃ for 1 hour; next, post-curing was carried out at 90 ℃ for 8 hours while polymerizing according to Table 1.

Example 3(polyester and MMA solution + 0.3% TiO)₂+ ATH) (inventive)

370.00 grams of POLYLITE 32166-16REICHHOLD polyester;

60 g of high-purity methyl methacrylate;

6 g of silane DYNASYLAN MEMO 3-trimethoxysilyl) propyl methacrylate;

3 g of TiO produced by DEGUSSA₂P-25；

549.92 g of ATH (alumina trihydrate) mineral filler, size less than 50 μm

-2.25, 1.5, 6 grams of cross-linking agent, EGDM-TEGDM-TMPTM respectively;

1.20 g of zinc stearate.

It can be seen that in all of the samples of examples 1, 2 and 3, the silane was in TiO form₂Two times the percentage amount added. TiO 2₂Dispersion and catalyst dispersion from TiO₂Nanometer size of P-25 (average diameter of about 21nm) and the combination with TiO₂The presence of siloxane groups provided in excess over the siloxane groups.

Can be carried out by passing TiO in the presence of the siloxane function of 3- (trimethoxysilyl) propyl methacrylate₂The dispersion of mass of (a) yields a polymeric material having a self-cleaning surface. Siloxane groups allow the addition of TiO₂Anchored to the structure of the polymeric material and at the same time acting as a dispersant.

Example 4(PMMA/MMA (syrup) + 0.3% TiO₂+ quartz) (composition described in WO 2013/017651) with chemical catalysis

The same formulation as in example 1 was chemically polymerized with a series of suitable catalysts which started to react at ambient temperature. They are:

TBPM t-butyl peroxymaleate PM-25 produced by Pergan PEROXAN, in a percentage of 0.5% to 2.0%, i.e. 1%

·Ca(OH)₂The percentage is 0.5 percent to 0.1 percent, namely 0.6 percent

Produced by BRUNO BOCK

PETMP pentaerythritol tetra (3-mercaptopropionate) accounting for 0.1 to 1.0 percent, namely 0.2 percent

Example 5(polyester and MMA solution + 0.3% TiO)₂+ ATH) (invention) and chemical catalysis

The same formulation as in example 3 was chemically polymerized with a series of suitable catalysts which started to react at ambient temperature. The catalyst may be:

·Ca(OH)₂The percentage is 0.5 percent to 0.1 percent, namely 0.6 percent

Produced by BRUNO BOCK

Comparative testing of polymeric composite samples

1.TiO₂Photocatalytic activity

Photocatalytic activity is tested by assessing the discoloration of organic colorants such as eosin and methylene blue, which mimic natural colorants commonly used for cooking, such as wine, vinegar, strawberry and other stains, which are placed on a composite surface,

a) self-cleaning of surfaces stained with eosin;

b) self-cleaning the surface dyed with methylene blue;

with eosin and methylene blueThe self-cleaning of dyed surfaces allows the assessment of TiO₂The ability to degrade certain colorants, such as eosin and methylene blue.

Examples 1 and 4, 2 and 3 and 5 (0.3% photocatalytic TiO) were examined₂And mineral fillers). By mixing examples 1 and 4, 2 and 3 and 5 (0.3% photocatalytic TiO)₂) The photocatalytic activity was checked by immersing the complex in a 0.0025M solution of methylene blue and eosin Y and measuring the time required to degrade the colorant. Xenon lamp (SolarBox 1500, 25 mW/cm)²λ 280-400 nm, outdoor filter) and monitoring the coloration by colorimetric measurement (ColorI 7X-Rite). Measurements were taken after 60, 90, 150, 210 and 270 minutes of exposure and colorimetric changes were expressed as a function of Δ Ε.

TABLE 2

Table 2 and FIG. 2 show the composite samples from examples 1 and 4, the sample from example 2 and the samples from examples 3 and 5 (0.3% photocatalytic TiO)₂And mineral fillers).

TABLE 3

Table 3 and FIG. 3 show the samples from examples 1 and 4, the sample from example 2 and the samples from examples 3 and 5 (0.3% photocatalytic TiO)₂And mineral fillers).

Based on the test results, the colorant was coated with TiO₂Degrading; this is a very important result, since it allows the surface of the materials from examples 1 and 4, 2 and 3 and 5 to be defined as self-cleaning; in addition, TiO was confirmed₂In comparison with examples 2 and 3 and 5 according to the inventionStructural bonding of polyester resin because TiO, like example 1 according to the prior art₂Appear on the surface of the methacrylic syrup.

In all tests, TiO was included₂Show high TiO₂Dispersibility and homogeneity, without decantation, as indicated by the chromaticity coordinates, that is to say the colour change of the dispersion to evaluate the dispersion homogeneity in the tests of table 4 below.

		ΔE
			Example 1	Slurry composite + 0.3% TiO₂+ quartz	0.50
Example 2	Polyester composite + 0.3% TiO₂+ATH	0.60
			Example 3	polyester-MMA Complex + 0.3% TiO₂+ATH	0.40
Example 4	Slurry composite + 0.3% TiO₂+ chemical catalysis with quartz	0.50
			Example 5	polyester-MMA Complex + 0.3% TiO₂+ ATH chemical catalysis	0.40

TABLE 4

2. Viscosity change with silane addition

To evaluate the chemical bond of silane to polyester resin, silane and TiO of examples 1, 2 and 3 were measured₂Viscosity at 0, 60 and 120 minutes in a ratio of 1: 2.

Adding silane to polyester resin or polyester resin and MMA and adding TiO₂After that, a significant change in the viscosity of the resin was found. This change confirmed TiO₂There is a direct interaction phenomenon with silane. Measurement of TiO by viscosity number of dispersions of different added silanes₂The results of the silanization time are shown in table 5 below and fig. 4.

TABLE 5

The viscosity values were measured at a temperature of about 20 ℃. As shown in table 5 and fig. 4, all examples show a clear change in viscosity upon addition of silane, which is a clear indication of the establishment of chemical bonds. The data show that after the first 60 minutes, the higher viscosity decrease is more pronounced, which is a clear indication that chemical bonds are established within such a period of time.

3. Visible cross-linking of the surface of the final product

In this test, the final product was a sink obtained from the dispersions of examples 1, 2 and 3. In the three final products, the cross-linking was visible to the naked eye, as the sink surface showed a highly reticulated, very matte surface with a very high aesthetic appearance. Such a surface is very different from a surface without titanium dioxide, which, in contrast, is very polished, has a non-uniform opacity and poor crosslinking.

4. Hardness and thermoformability

Hardness and thermoformability tests were performed on the samples of examples 1, 2, 3, 4 and 5, as shown in tables 6 and 7 below, respectively. Hardness was measured in HRM.

	Hardness of	HRM
			Example 1	Slurry composite + 0.3% TiO₂+ quartz	105.00
Example 2	Polyester composite + 0.3% TiO₂+ATH	90.00
			Example 3	polyester-MMA Complex + 0.3% TiO₂+ATH	92.00
Example 4	Slurry composite + 0.3% TiO₂+ chemical catalysis with quartz	104.00
			Example 5	polyester-MMA Complex + 0.3% TiO₂+ ATH chemical catalysis	93.00

TABLE 6

As shown in table 6, the samples according to examples 2 and 3 and 5 of the present invention have a characteristic of low hardness as compared with the sample according to example 1 of the related art. Thus, samples 2 and 3 and 5 are easy to process, while samples 1 and 4 are difficult to process.

	Thermo-forming	Degree of curvature
			Examples 1 and 4	Slurry composite + 0.3% TiO₂+ quartz	0°
Example 2	Polyester composite + 0.3% TiO₂+ATH	25°
			Examples 3 and 5	polyester-MMA Complex + 0.3% TiO₂+ATH	24°

TABLE 7

As shown in table 7, the samples of examples 2 and 3 and 5 according to the present invention have a curvature of more than 20 °, whereas the samples of examples 1 to 4 have no curvature. Curvature is the angle that can be formed from a flat surface, which can be considered to be an angle of 0.

Thus, samples 2a and 3 and 5 were thermoformable, whereas samples 1 and 4 were not thermoformable.

Many variations and modifications can be made to the present embodiment of the invention which are within the reach of the expert in the field and in any case fall within the scope of the invention as disclosed in the appended claims.

Claims

1. A self-cleaning composite comprising the following composition:

-50-85% by weight of a mineral filler;

-10-30% of a polymer;

-photocatalytic titanium dioxide (TiO) dispersed in the polymer in a percentage by weight ranging from 0.05% to 5% with respect to the weight of the polymer₂)；

For anchoring in photocatalytic TiO₂A compatibilizer with the polymer, wherein the TiO₂The anchoring compatibilizer of (a) is a silane; and

-a crosslinking monomer for obtaining crosslinking of the polymer,

characterised in that the mineral filler comprises Alumina Trihydrate (ATH) and the polymer comprises a polyester resin.

2. The self-cleaning composite material of claim 1, wherein said Alumina Trihydrate (ATH) has a particle size of 10-50 microns.

3. The self-cleaning composite material according to claim 1 or 2, wherein Methyl Methacrylate (MMA) is added to the polyester resin in a weight percentage lower than 15% of the weight of the mixture of polyester resin and Methyl Methacrylate (MMA).

4. The self-cleaning composite material according to claim 1 or 2, wherein said silane is 3- (trimethoxysilyl) propyl methacrylate, said silane being in contrast to photocatalytic TiO₂Twice as much.

5. The self-cleaning composite material of claim 1 or 2, wherein the composition further comprises a silylation catalyst.

6. The self-cleaning composite material of claim 5, wherein said silylation catalyst is Isopropylamine (IPA) and/or methacrylic acid.

7. The self-cleaning composite material according to claim 1 or 2, wherein the photocatalytic titanium dioxide is in anatase form and is a powder having a particle size of less than 300 nm.

8. Self-cleaning composite material according to claim 1 or 2, characterized in that said crosslinking monomers comprise Ethylene Glycol Dimethacrylate (EGDM), tetraethylene glycol dimethacrylate (TEGDM) and trimethylolpropane trimethacrylate (TMPTMA).

9. Self-cleaning composite material according to claim 1 or 2, characterized in that it further comprises fine particles of the silicate family having a particle size of less than 0.1mm, in a percentage by weight of between 2% and 15% with respect to the weight of the total composition.

10. Self-cleaning composite material according to claim 9, characterized in that the fine particles of the silicate group are quartz and/or hollow or solid glass microspheres.

11. A method of making a self-cleaning composite material comprising the steps of:

-preparing a polyester resin in an amount corresponding to 10% to 30% by weight of the final product;

-dispersing a silane in the polyester resin;

-stirring a mixture of polyester resin and silane;

photocatalytic titanium dioxide (TiO) in a percentage by weight ranging from 0.05% to 5% with respect to the weight of the polyester resin₂) Dispersed in a mixture of a polyester resin and a silane;

stirring of polyester resin, silane and titanium dioxide (TiO)₂) A mixture of (a);

-adding to the mixture the following components: 50-85% by weight of an Alumina Trihydrate (ATH) mineral filler and a crosslinking monomer to obtain a network structure of the polyester resin;

-stirring the final mixture;

-polymerizing the mixture in a mould.

12. The method of claim 11, wherein the silane is applied against photocatalytic TiO₂Twice as much.

13. The method of claim 11 or 12, wherein the step of agitating the mixture of polyester resin and silane and the polyester resin, silane and titanium dioxide (TiO)₂) The stirring step of the mixture of (1) was carried out with a screw stirrer at 900rpm and 1800rpm for 30 minutes and 2.5 hours, respectively, and then the other components were added.

14. The method of claim 11 or 12, wherein the step of polymerizing in a mold is performed by a gradual increase to 100 ℃ over 8 hours at an initial temperature of 50 ℃.

15. The method of claim 11 or 12, wherein the step of polymerizing is carried out by a chemical reaction at room temperature over one or more of the following catalysts:

t-butyl peroxymaleate, in a percentage from 0.5% to 2.0%,

Ca(OH)₂(calcium hydroxide) in a percentage of 0.5% to 1.0%,

PETMP (pentaerythritol tetrakis (3-mercaptopropionate)), in percentages ranging from 0.1% to 1.0%.